WO2020181022A1 - Acides polyamiques et polyimides coiffés par anhydride cyclique insaturé terminal et compositions photosensibles associées - Google Patents

Acides polyamiques et polyimides coiffés par anhydride cyclique insaturé terminal et compositions photosensibles associées Download PDF

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WO2020181022A1
WO2020181022A1 PCT/US2020/021049 US2020021049W WO2020181022A1 WO 2020181022 A1 WO2020181022 A1 WO 2020181022A1 US 2020021049 W US2020021049 W US 2020021049W WO 2020181022 A1 WO2020181022 A1 WO 2020181022A1
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bis
group
polyimide
diyl
dione
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PCT/US2020/021049
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English (en)
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Pramod Kandanarachchi
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Promerus, Llc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides

Definitions

  • the present invention relates to a series of unsaturated cyclic anhydride end capped polyamic acid and polyimide polymers. More specifically, the present invention relates to a photosensitive composition containing unsaturated cyclic anhydride, such as itaconic anhydride end capped polyamic acid and polyimide polymers.
  • the compositions of this invention are useful for forming microelectronic and/or optoelectronic devices and assemblies thereof, and more specifically, such compositions exhibit improved thermal, mechanical and opto-electronic properties.
  • Organic polymer materials are increasingly being used in the microelectronics and optoelectronics industries for a variety of applications.
  • the uses for such organic polymer materials include permanent interlevel dielectrics, redistribution layers (RDL), stress buffer layers, chip stacking and/or bonding, leveling or planarization layers, alpha-particle barriers, passivation layers, among others, in the fabrication of a variety of microelectronic and optoelectronic devices.
  • RDL redistribution layers
  • stress buffer layers chip stacking and/or bonding
  • leveling or planarization layers alpha-particle barriers
  • passivation layers among others.
  • organic polymer materials are photosensitive, thus self-imageable, and therefore, offer additional advantage of reducing the number of processing steps required for the use of such layers and structures made therefrom.
  • organic polymer materials enable the direct adhesive bonding of devices and device components to form various structures.
  • Such devices include microelectromechanical systems (MEMS), microoptoelectromechanical systems (
  • polyimides and its precursor, polyamic acid.
  • polyimides are generally for positive tone image forming films, and many not suitable for many applications.
  • Some of the drawbacks include use of highly toxic and corrosive phenolic monomers which provide alkali solubility that is required for forming positive tone compositions.
  • Other property disadvantages include insolubility of the polyimides and/or the precursor polyamic acids in commonly used solvents in the electronic industry, poor photo imaging capabilities, among others. Even more importantly, such compositions suffer from poor thermo-mechanical properties and may require high cure temperatures, often times higher than 300 °C, which are undesirable. See for example, U. S. Patent No. 8,946,852 B2 and U. S. Patent No. 7,485,405 B2.
  • thermo-mechanical properties it is an object of this invention to provide a series of unsaturated cyclic anhydride end capped polyamic acid and polyimide polymers and their compositions that provide improved thermo-mechanical properties.
  • the polyamic acid and polyimide polymers as disclosed herein can be made by employing any of the known dianhydrides and diamines in combination with a substituted unsaturated cyclic anhydride to produce unsaturated cyclic anhydride capped polyamic acid or polyimide, which are soluble in commonly used organic solvents.
  • the polymers of this invention can then be combined with a number of additives to form photosensitive compositions which feature excellent thermomechanical properties, photo-imaging properties, low cure temperatures, generally below 250°C or lower, among other property enhancements.
  • FIGs. 1 to 3 show top down optical micrograph images of a composition embodiment of this invention. DETAILED DESCRIPTION OF THE INVENTION
  • the articles“a,”“an,” and“the” include plural referents unless otherwise expressly and unequivocally limited to one referent.
  • ranges are continuous, inclusive of both the minimum and maximum values of the range as well as every value between such minimum and maximum values. Still further, where a range refers to integers, every integer between the minimum and maximum values of such range is included. In addition, where multiple ranges are provided to describe a feature or characteristic, such ranges can be combined. That is to say that, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. For example, a stated range of from“1 to 10” should be considered to include any and all sub-ranges between the minimum value of 1 and the maximum value of 10. Exemplary sub-ranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, etc.
  • alkyl means a saturated, straight-chain or branched- chain hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl, tert-butyl, and so on. Derived expressions such as “alkoxy”,“thioalkyl”,“alkoxyalkyl”,“hydroxyalkyl”,“alkylcarbonyl”,“alkoxycarbonylalkyl”, “alkoxycarbonyl”,“diphenylalkyl”,“phenylalkyl”,“phenylcarboxyalkyl” and“phenoxyalkyl” are to be construed accordingly.
  • cycloalkyl includes all of the known cyclic groups.
  • Representative examples of “cycloalkyl” includes without any limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • Derived expressions such as“cycloalkoxy”,“cycloalkylalkyl”,“cycloalkylaryl”,“cycloalkylcarbonyl” are to be construed accordingly.
  • the expression“perhaloalkyl” represents the alkyl, as defined above, wherein all of the hydrogen atoms in said alkyl group are replaced with halogen atoms selected from fluorine, chlorine, bromine or iodine.
  • Illustrative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, and straight-chained or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, and the like.
  • alkyl groups as described herein such as for example,“alkyl” may partially be fluorinated, that is, only portions of the hydrogen atoms in said alkyl group are replaced with fluorine atoms and shall be construed accordingly.
  • “acyl” shall have the same meaning as“alkanoyl”, which can also be represented structurally as“R-CO-,” where R is an“alkyl” as defined herein having the specified number of carbon atoms. Additionally,“alkylcarbonyl” shall mean same as“acyl” as defined herein. Specifically,“(C 1 -C 4 )acyl” shall mean formyl, acetyl or ethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as“acyloxy” and“acyloxyalkyl” are to be construed accordingly.
  • aryl means substituted or unsubstituted phenyl or naphthyl.
  • substituted phenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc.
  • Substituted phenyl or “substituted naphthyl” also include any of the possible substituents as further defined herein or one known in the art.
  • arylalkyl means that the aryl as defined herein is further attached to alkyl as defined herein.
  • Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.
  • alkenyl means a non-cyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, and includes ethenyl and straight-chained or branched propenyl, butenyl, pentenyl, hexenyl, and the like.
  • Derived expression,“arylalkenyl” and five membered or six membered“heteroarylalkenyl” is to be construed accordingly.
  • Illustrative examples of such derived expressions include furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.
  • heteroaryl includes all of the known heteroatom containing aromatic radicals.
  • Representative 5-membered heteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like.
  • Representative 6-membered heteroaryl radicals include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like radicals.
  • bicyclic heteroaryl radicals include, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like radicals.
  • heterocycle includes all of the known reduced heteroatom containing cyclic radicals.
  • Representative 5-membered heterocycle radicals include tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like.
  • Representative 6-membered heterocycle radicals include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like.
  • Various other heterocycle radicals include, without limitation, aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hept-2- yl, and triazocanyl, and the like.
  • Halogen or“halo” means chloro, fluoro, bromo, and iodo.
  • the term“substituted” is contemplated to include all permissible substituents of organic compounds.
  • the term“substituted” means substituted with one or more substituents independently selected from the group consisting of (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 1 .C 6 )perfluoroalkyl, phenyl, hydroxy, -CO 2 H, an ester, an amide, (C 1 .C 6 )alkoxy, (C 1 .C 6 )thioalkyl and (Ci.C 6 )perfluoroalkoxy.
  • any of the other suitable substituents known to one skilled in the art can also be used in these embodiments.
  • dielectric and“insulating” are used interchangeably herein.
  • reference to an insulating material or layer is inclusive of a dielectric material or layer and vice versa.
  • microelectronic device is inclusive of a“micro-optoelectronic device” and an “optoelectronic device”.
  • reference to microelectronic devices or a microelectronic device assemblies are inclusive of optoelectronic devices and micro-optoelectronic devices as well as assemblies thereof.
  • RDL distributed layer
  • polymer composition As used herein, the terms “polymer composition,” “copolymer composition,” “terpolymer composition” or“tetrapolymer composition” are used herein interchangeably and are meant to include at least one synthesized polymer, copolymer, terpolymer or tetrapolymer, as well as residues from initiators, solvents or other elements attendant to the synthesis of such polymers, where such residues are understood as not necessarily being covalently incorporated thereto. But some catalysts or initiators may sometimes be covalently bound to a part of the polymeric chain either at the beginning and/or end of the polymeric chain.
  • a polymer composition can also include materials added after synthesis of the polymer to provide or modify specific properties of such composition. Such materials include, but are not limited to solvent(s), antioxidant(s), photoinitiator(s), sensitizers and other materials as will be discussed more fully below.
  • modulus is understood to mean the ratio of stress to strain and unless otherwise indicated, refers to the Young’s Modulus or Tensile Modulus measured in the linear elastic region of the stress-strain curve. Modulus values are generally measured in accordance with ASTM method DI708-95. Films having a low modulus are understood to also have low internal stress.
  • photodefinable refers to the characteristic of a material or composition of materials, such as a polymer or polymer composition in accordance with embodiments of the present invention, to be formed into, in and of itself, a patterned layer or a structure.
  • a“photodefinable layer” does not require the use of another material layer formed thereover, for example, a photoresist layer, to form the aforementioned patterned layer or structure.
  • a polymer composition having such a characteristic is generally employed in a pattern forming scheme to form a patterned film/layer or structure. It will be noted that such a scheme incorporates an “imagewise exposure” of the photodefinable material or layer formed therefrom. Such imagewise exposure being taken to mean an exposure to actinic radiation of selected portions of the layer, where non-selected portions are protected from such exposure to actinic radiation.
  • the term“self-imageable compositions” will be understood to mean a material that is photodefinable and can thus provide patterned layers and/or structures after direct image-wise exposure of a film formed thereof followed by development of such images in the film using an appropriate developer.
  • derived is meant that the polymeric repeating units are formed from, for example, condensation of a dianhydride with a diamine. That is, polyimide repeat units are derived from the corresponding dianhydride and diamine. Generally, such condensation reaction first results in a polyamic acid which is further condensed to form a polyimide as described further in detail below.
  • a polyamic acid or a polyimide is generally derived from the condensation of equimolar amounts of at least one dianhydride with one diamine.
  • a mono-anhydride or a mono-amine is used off-setting the stoichiometry, the resulting polyimide will be end-capped with such excess amount of either the mono-anhydride or the mono-amine employed.
  • n is an integer of at least 50;
  • X is one or more distinct tetravalent organic group
  • Y is one or more distinct divalent organic group
  • R 1 and R 2 are the same or different and each independently of one another selected from the group consisting of linear or branched (C 1 .C 6 ) alkenyl, hydroxy(C 1 -C 12 )alkenyl, perfluoro(C 1 -C 12 )alkenyl, and (C 6 -C 10 )aryl(C1-C3)alkenyl.
  • the polyamic acid of formula (IA) or polyimide of formula (IB) of this invention can be synthesized by any of the procedures known to one skilled in the art. As noted above, such methods include condensation of one or more dianhydrides with one or more diamines essentially in equimolar ratios. Further, suitable amounts of substituted unsaturated cyclic anhydride of formula (II) is employed to end cap the resulting polyamic acid or polyimide. Any of the dianhydrides or diamines in combination with substituted cyclic anhydride or their equivalent precursor compounds can be employed. More specifically, the dianhydrides and the diamines that are suitable for forming the polyamic acid or polyimide of this invention can be represented by the following general formulae (IC) and (ID).
  • any of the dianhydrides of tetracarboxylic acids in combination with any of the diamines can be employed to form the polyamic acid and subsequently the polyimides.
  • any of the techniques known in the art to make polyimides and/or polyamic acid can be employed herein in combination with desirable amounts of the cyclic anhydride of formula (II).
  • any of the suitable tetravalent organic group can be employed herein.
  • Non-limiting examples of such X may be selected from the group consisting of:
  • a is an integer from 0 to 4, inclusive
  • each of R 3 is independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, trifluoromethyl, pentafluoroethyl, linear or branched perfluoro(C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, phenyl and phenoxy;
  • Z is a divalent group selected from the group consisting of: (CR 4 R 5 ) b , O(CR 4 R 5 ) b , (CR 4 R 5 ) b O, (OCR 4 R 5 )d, (CR 4 R 5 0) d , (CR 4 R 5 ) b -0-(CR 4 R 5 ) c , (CR 4 R 5 ) b -0-(SiR 4 R 5 ) c , (CR 4 R 5 ) b -(C0)0-(CR 4 R 5 ) c , (CR 4 R 5 ) b -0(CO)-(CR 4 R 5 ) c ,
  • R 4 and R 5 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, trifluoromethyl, pentafluoroethyl, linear or branched perfluoro(C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, phenyl and phenoxy.
  • Suitable dianhydrides may include the following:
  • the polyimide or polyamic acid of this invention are formed using the dianhydrides where X is derived from one or more dianhydrides selected from the group consisting of:
  • any of the diamines known in the art can be used to form the polyamide or polyamic acid of this invention.
  • the diamines can again be broadly classified as aromatic diamines, aliphatic diamines or mixed aliphatic-aromatic diamines which contain a wide variety of bridging groups.
  • a non-limiting generic types of diamines include the following:
  • the polyimide or polyamic acid of this invention are formed using the diamines where Y is derived from one or more diamines selected from the group consisting of:
  • polyamic acid or polyimide of this invention are end capped with a suitable unsaturated cyclic anhydride.
  • a suitable end capped unsaturated cyclic anhydride group is derived from a compound of formula (
  • R 1 and R 2 are as defined in claim 1.
  • any of the unsaturated cyclic anhydride of formula (II) that will bring about the intended benefit can be employed herein.
  • Non-limiting examples of the compound of formula (II) is selected from the group consisting of:
  • the polyamic acid or the polyimide of this invention having suitable molecular weight can be tailored based on the intended application by employing appropriate polycondensation methods. Accordingly, in some embodiments the number of repeat units, m, in the resulting polyamic acid or the polyimide is at least 50; in some other embodiments m is at least 100, 500, 1000, 2000 or higher. In some embodiments m is from 50 to 2000, inclusive.
  • the degree of polycondensation can be measured by determining the molecular weight of the resulting polyamic acid or the polyimide using any of the known methods in the art, such as for example, by gel permeation chromatography (GPC) equipped with suitable detector and calibration standards, such as differential refractive index detector calibrated with narrow-distribution polystyrene standards.
  • GPC gel permeation chromatography
  • the polyamic acid or the polyimide of this invention generally exhibit a weight average molecular weight (M w ) of at least about 5,000.
  • the polyamic acid or polyimide as described herein exhibit a weight average molecular weight (M ) of at least about 20,000.
  • the polyamic acid or polyimide made in accordance of this invention has a M w of at least about 50,000.
  • the polyamic acid or polyimide of this invention has a M w of at least about 100,000.
  • the polyamic acid or polyimide of this invention has a M w of at least about 200,000.
  • the polyamic acid or polyimide of this invention has a M w ranging from about 50,000 to 500,000, or higher.
  • the polyamic acid or polyimide of this invention generally contains an amic acid or imide repeat unit derived from at least one dianhydride and at least one diamine end capped with a cyclic anhydride of formula (II) as described herein.
  • the polyamic acid or the polyimide of this invention contains an amic acid or imide repeat units derived from two or more anhydrides and two or more diamines as described herein, which is further end capped with the cyclic anhydride of formula (II) as described herein. All of such permutation and combinations are part of this invention.
  • equimolar ratios of dianhydrides and diamines are employed to form the polyamic acid or the polyimide.
  • the polyamic acid or the polyimide of this invention contains generally equal molar amounts of the total dianhydride and the total diamines when more than one dianhydride or more than one diamine is employed. That is, a polyamic or the polyimide of this invention is made by employing equimolar amounts of dianhydride and diamine, which includes the molar amounts of the end capped cyclic anhydride of formula (II).
  • Non-limiting examples of a polyamic acid or a polyimide made in accordance of this invention may be enumerated as follows:
  • organic solvents are selected from the group consisting of N-methy1-2-pyrrolidone (NMP), g-butyrolactone (GBL), N,N-dimethylacetamide (DMAc), propylene glycol monomethyl ether acetate (PGMEA), dimethyl sulfoxide (DMSO), cyclopentanone, cyclohexanone, 2-butanone and 2-heptanone and mixtures in any combination thereof.
  • NMP N-methy1-2-pyrrolidone
  • GBL g-butyrolactone
  • DMAc N,N-dimethylacetamide
  • PMEA propylene glycol monomethyl ether acetate
  • DMSO dimethyl sulfoxide
  • any of the aforementioned solvents can be used alone or in combination with one or more solvents.
  • the polyimides of this invention exhibit very high thermo-mechanical properties. Specifically, it has now been found that the films formed from the polyimides of this invention exhibit excellent tensile properties as well as very high elongation to break (ETB).
  • the films can be readily formed from any of the known solvent casting methods as well as melt extrusion methods.
  • the polyamic acid or polyimide of this invention can be coated onto a suitable substrate, such as for example, spin coating. The coated substrates are then baked to remove any residual solvents especially in the case of polyimide coated substrate. The polyamic acid coated substrates are further baked to form the polyimide at a suitable temperature.
  • Such post apply baking (PAB) temperatures can range from about 100 °C to 150 °C for a sufficient length of time from about 2 minutes to 30 minutes. In some embodiments such PAB temperature is at about 110 °C for about 3 minutes.
  • the polyamic acid films so formed are then cured at a temperature in the range of from about 280 °C to 350 °C to form the polyimide films for a sufficient length of time ranging from about 2 hours to 4 hours under inert atmosphere, such as for example, nitrogen atmosphere. In some embodiments such curing is carried out at 320 °C for about 3 hours.
  • the films of polyimide polymers of this invention can be formed directly from the solutions of the respective polyimide polymers by casting on to a suitable substrate.
  • the polyimide polymer coated substrates are post apply baked (PAB) at temperatures ranging from about 100 °C to 150 °C for a sufficient length of time, typically, from about 2 minutes to 30 minutes. In some embodiments such PAB temperature is at about 110 °C for about 3 minutes.
  • PAB temperature is at about 110 °C for about 3 minutes.
  • the polyimide films so formed are then cured at a significantly lower temperature than mentioned above, such as for example in the temperature range of from about 150 °C to 250 °C to form the fully cured polyimide films for a sufficient length of time ranging from about 2 hours to 6 hours under inert atmosphere, such as for example, nitrogen atmosphere. In some embodiments such curing is carried out at 170 °C for about 4 hours. In some other embodiments such curing is carried out at 220 °C for about 3 to 4 hours.
  • the cured polyimide films can readily be lifted out of the substrates for mechanical property testing.
  • the tensile strength of the so formed films are generally in the range from about 100 MPa to about 250 MPa depending upon the type of dianhydrides and diamines employed to form the polyimide. In some embodiments the tensile strength is from about 150 MPa to about 200 MPa and in some other embodiments the tensile strength is from about 160 MPa to about 180 MPa.
  • the ETB of the films are generally high as well. The ETB can range from about 30 percent to 100 percent or higher. In some embodiments the ETB ranges from about 40 percent to 90 percent, 50 percent to 80 percent, and so on.
  • compositions of this invention comprising the polyamic acid or the polyimide of formulae (IA) or (IB) as described herein in combination with a photo radical generator and a thermal radical generator.
  • the compositions of this invention are photosensitive, and therefore, can be employed in a variety of optoelectronic application for forming a variety of polymeric layers, which may be pattemable so as to find applications as dielectric materials.
  • composition of this invention encompasses all of the polyamic acids and polyimides as described hereinabove derived from any of the dianhydrides, diamines, and end capped with a unsaturated cyclic anhydride as described hereinabove and hereafter, including the specific polyamic acids and the polyimides enumerated above and specifically exemplified below.
  • the composition of this invention encompasses a photo radical generator selected from the group consisting of:
  • R 6 and R 7 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C1-C8)alkyl and (C 6 -C 10 )aryl, or R 6 and R taken together with the nitrogen atom to which they are attached to form a 5 to 7 membered monocyclic ring or 6 to 12 membered bicyclic ring, said ring optionally containing one or more heteroatoms selected from O and N, and said ring optionally substituted with a group selected from the group consisting of linear or branched (C 1 -C 8 )alkyl, (C 6 -C 10 )aryl, halogen, hydroxy, linear or branched (C 1 -C 8 )alkoxy and (C 6 -C 10 )aryloxy; and
  • R 8 , R. 9 and R 1 o are the same or different and each independently of one another is selected from the group consisting of hydrogen, linear or branched (C 1 .C 6 ) alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, hydroxy, halogen, linear or branched (C 1 -C 12 )alkoxy and (C 6 -C 10 )aryloxy; and
  • d is an integer from 0 to 3, inclusive;
  • R 1 i is selected from the group consisting of hydrogen, linear or branched (C i -Chalky 1, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, hydroxy, halogen, linear or branched (C 1 -C 12 )alkoxy and (C 6 -C 10 )aryloxy;
  • R 12 is selected from the group consisting of linear or branched (Ci-Ci6)alkyl
  • (C 6 -C 10 )aryl (C 1 .C 6 )alkylphosphinate, (C 6 -C 10 )heterocycle(C 1 -C 3 )alkyl, a group of formula C(0)-(OCH 2 CH 2 ) c -OC(0)C(0)(C 6 -C 10 )aryl, where e is an integer from 2 to 4, inclusive, C(0)C(0)0(C 1 -C 3 )alkyl and a group of formula (C):
  • R 1 3 is linear or branched (C 1 .C 6 ) alkyl
  • 4 is (C 6 -C 10 )aryl
  • alkyl, cycloalkyl, aryl and heterocycle may additionally be substituted with one or more groups selected from the group consisting of hydroxy, linear or branched (C 1 .C 6 )alkyl, linear or branched (C 1 .C 6 )alkoxy and linear or branched
  • Non-limiting examples of the photo radical generator are enumerated as follows:
  • benzophenone commercially available as DAROCUR BP from Ciba Specialty Chemicals
  • the composition of this invention contains two or more photo radical generators selected from the above list. Any of the suitable amounts of the photo radical generator can be employed in the composition of this invention which will bring about the intended effect. Generally, such amounts may vary from about 5 parts per hundred parts resin (pphr) to about 15 pphr or higher. In some embodiments the amount of photo radical generator employed is from about 8 pphr to about 12 pphr.
  • composition of this invention further includes a thermal radical initiator.
  • a thermal radical initiator Any of the compounds which when exposed to heat forms a radical can be employed for this purpose. Suitable generic classes of such compounds include peroxides, peracids, azo compounds, N- alkoxyamines, N-acyloxyamines, and the like.
  • Non-limiting examples of such specific thermal radical generators include benzoyl peroxide, dicumyl peroxide, m-chloroperbenzoic acid, methyl ethyl ketone peroxide, azobisisobutyronitrile (AIBN), (1 -phenyl-3,3- dipropyltriazene), (1- (phenyldiazenyl)pyrrolidine), (1-(phenyldiazenyl)piperidine), (1-(phenyldiazenyl)azepane) and the like.
  • AIBN azobisisobutyronitrile
  • any of the suitable amounts of the thermal radical generator can be employed in the composition of this invention which will bring about the intended effect. Generally, such amounts may vary from about 2 parts per hundred parts resin (pphr) to about 10 pphr or higher. In some embodiments the amount of photo radical generator employed is from about 3 pphr to about 6 pphr.
  • any suitable sensitizer compound can be employed in the compositions of the present invention.
  • suitable sensitizer compounds include, photosensitizers, such as, anthracenes, phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes, xanthones, indanthrenes, and mixtures thereof.
  • suitable sensitizer components include mixtures thereof.
  • the photosensitizers absorb energy from the radiated light source and transfers that energy to the photo radical generator of formulae (IV) or (V) employed in the composition of this invention so as to generate the radicals to initiate the crosslinking.
  • the photosensitizer as employed herein may itself act as a photo radical generator.
  • the composition of this invention contains only one or more photosensitizers, which not only activates the composition at certain wavelength but also generates photo radical triggering the crosslinking.
  • the composition of this invention contains one or more photo radical generators of formulae (IV) or (V) in combination with one or more photosensitizers of formula (VI) as described hereinbelow.
  • composition of this invention contains one or more of a photosensitizer of the formula (VI):
  • R 15 and R 16 are the same or different and independently of each other selected from the group consisting of hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl,
  • Non-limiting examples of suitable one or more photosensitizers may be selected from the group consisting of:
  • any one of these compounds can be used as photosensitizers alone or as mixtures in any combination thereof, and only if needed depending upon the intended use and to obtain the desirable benefit.
  • any amount of one or more of aforementioned sensitizers can be used in the composition of this invention so as to bring about the desired results.
  • such amounts can range from 0.5 to 5 parts per hundred parts of the polymer resin (pphr). In some embodiments such amounts range from 1 to 3 pphr.
  • compositions of the present invention also include one or more crosslinking agents that are advantageously capable of bonding with the end-capped substituted unsaturated cyclic imide group of the polyamic acid or polyimide or any other functional group available in the polymeric chain for further crosslinking when exposed to a suitable radiation.
  • crosslinking compounds include, but are not limited to, crosslinking compounds that incorporate one or more of an oxazoline group such as 2-oxazoline-2-yl group, a methylol group such as a N-hydroxy methylaminocarbonyl group or an alkoxymethyl group such as a N-methoxy methylaminocarbonyl group, acrylate group, thiol or thioalkyl group, maleimide, and the like.
  • the aforementioned bonding with the substituted unsaturated cyclic imide end group of the polyimide is a cross-linking reaction that is initiated by photo radical generated during the photo-irradiation at an appropriate temperature.
  • crosslinking can be completed further by curing at an appropriate temperature post irradiation, generally at or above 150°C for an appropriate amount of time.
  • thermal curing is further facilitated by thermal radical generator as well as the thermal crosslinking agents such as for example, epoxy groups such as a glycidyl group, an epoxycyclohexyl group, an oxetane group, and the like. It should be noted however that it is surprising that such curing of the composition of this invention can be carried out at much lower temperature than conventionally used for polyimides known in the art, which is generally carried out at higher than 250 °C or even higher than 300 °C.
  • the photosensitive composition of this invention contains one or more crosslinking agents selected from the following:
  • crosslinking agents that may be employed in the composition of this invention without any limitation may be selected from the group consisting of:
  • the photosensitive composition of this invention further encompasses one or more compounds or additives having utility as, among other things, adhesion promoter, a surface leveling agent, antioxidants, a synergist, silane coupling agents, phenolic resins, flame retardants, plasticizers, curing accelerators, and the like.
  • surface leveling agents include a variety of non-ionic, amphoteric and anionic surfactants available in the art, which provide, among other things, wetting, spreading and levelling properties.
  • Exemplary surface leveling agents include without any limitation, non-ionic polymeric fluorochemical surfactant, such as for example, FC-4432 available from 3M Advanced Materials Division, a short chain perfluoro-based ethoxylated nonionic fluorosurfactant, such as for example, Chemguard S-550, CAPSTONE fluorosurfactants available as both nonionic and amphoteric forms from DuPont, PolyFox fluorosurfactants from OMNOVA Solutions, and the like.
  • non-ionic polymeric fluorochemical surfactant such as for example, FC-4432 available from 3M Advanced Materials Division
  • a short chain perfluoro-based ethoxylated nonionic fluorosurfactant such as for example, Chemguard S-550, CAPSTONE fluorosurfactants available as both nonionic and amphoteric forms from DuPont, PolyFox fluorosurfactants from OMNOVA Solutions, and the like.
  • any of the known conventional surfactants may be used in combination with the above noted surfactants, such known non-ionic surfactants include for example, perfluoroalkyl polyoxyethylene ethanols, fluorinated alkyl esters, perfluoroalkylamine oxides and fluorinated organosiloxane compounds.
  • Various other such commercially available surfactants include Florade FC-4430 from Sumitomo 3M Ltd., Surflon S-141 and S-145 from Asahi Glass Co., Ltd., Unidyne DS-401, DS-4031 and DS-451 from Daikin Industries Ltd., Megaface F-8151 from Dainippon Ink & Chemicals, Inc., and X-70-093 from Shin-Etsu Chemical Co., Ltd.
  • Non-limiting examples of such other compounds or additives are selected from the group consisting of the following, commercially available materials are indicated by such commercial names.
  • triethoxy(3-(oxiran-2-ylmethoxy)propyl)silane also known as 3-glycidoxypropyl triethoxysilane (3-GTS or (KBE-403 from Shin-Etsu Chemical Co., Ltd.));
  • trimethoxy(3-(oxiran-2-ylmethoxy)propyl)silane also commonly known as
  • various compounds and additives as enumerated herein improve overall performance of the photosensitive composition of this invention thus providing well defined photo-patterned structures having a variety of utilities, including but not limited to chip-stack applications, redistribution layers (RDL) and for forming CMOS image sensor dam structures.
  • RDL redistribution layers
  • certain of the additives as described herein may feature more than one function.
  • some of the additives as enumerated hereinabove may not only exhibit certain photosensitization activity during exposure to radiation but may also facilitate as a cross linking agent as further described above. Therefore, additives as used herein do not limit the activity of such compounds to only one of such property but may also facilitate other functions of the photosensitive compositions of this invention.
  • the photosensitive composition embodiments are first applied to a desired substrate to form a film.
  • a substrate includes any appropriate substrate as is, or may be used for electrical, electronic or optoelectronic devices, for example, a semiconductor substrate, a ceramic substrate, a glass substrate.
  • any appropriate coating method can be employed, for example, spin coating, spraying, doctor blading, meniscus coating, inkjet coating and slot coating.
  • the coated substrate is heated to facilitate the removal of residual casting solvent, for example to a temperature from 70°C to 130°C for from 1 to 30 minutes, although other appropriate temperatures and times can be used.
  • the film is generally imagewise exposed to an appropriate wavelength of actinic radiation, wavelength is generally selected based on the choice of the photo radical generator and/or photosensitizer incorporated into the polymer composition as described herein. However, generally such appropriate wavelength is from 200 to 700 nm.
  • imagewise exposure means exposing through a masking element to provide for a resulting pattern of exposed and unexposed portion of the film, as further illustrated by specific examples hereinbelow.
  • a development process is employed.
  • such development process removes only the unexposed portions of the film thus leaving a negative image of the masking layer in the film.
  • a post exposure bake (PEB) is employed prior to the aforementioned development process, generally at a temperature from 90°C to 130°C for from 1 to 10 minutes, although other appropriate temperatures and times can be used.
  • Suitable developers can include organic solvents such as propylene glycol methyl ether acetate (PGMEA), 2-heptanone, cyclohexanone, NMP, GBL, cyclopentanone, butyl acetate, and mixtures in any combination thereof, among others.
  • PMEA propylene glycol methyl ether acetate
  • 2-heptanone 2-heptanone
  • cyclohexanone NMP
  • GBL cyclopentanone
  • butyl acetate cyclopentanone
  • composition embodiments of the present invention provide self-imageable films that after imagewise exposure, the resulting image is developed using an organic solvent.
  • the substrate is rinsed to remove excess developer solution, typical rinse agents are water or appropriate alcohols and mixtures thereof.
  • the excess developer can also be removed by blowing a stream of nitrogen on to the substrate.
  • Other methods of removing excess developer include spinning the developed wafer at high spin speeds of about 1000 - 3000 rpm for 10 - 30 sec followed by applying a stream of nitrogen.
  • the substrate is dried and the imaged film finally cured. That is to say, the image is fixed.
  • image fixing is generally accomplished by causing further reaction within the remaining portions of the film.
  • Such reaction is generally a cross-linking reaction that can be initiated by heating and/or non-imagewise or blanket exposure of the remaining material.
  • Such exposure and heating can be in separate steps or combined as is found appropriate for the specific use of the imaged film.
  • the blanket exposure is generally performed using the same energy source as employed in the imagewise exposure or a higher energy source and may be for a longer period of time although any other appropriate energy source can be employed.
  • the heating is generally carried out at a desirable temperature, for example, from above 150°C for a time of from 40 min to one or more hours.
  • image fixing is generally accomplished by a heating step to be tailored to complete any reaction initiated by the exposure.
  • an additional blanket exposure and heating as discussed above, can also be employed. It should be realized, however, that the choice of a final cure process is also a function of the type of device being formed; thus a final fixing of the image may not be a final cure where the remaining layer is to be used as an adhesive layer or structure.
  • the devices are produced by using embodiments of the composition of the present invention to form layers which are characterized as having high heat resistance, an appropriate water absorption rate, high transparency, and low permittivity.
  • such layers generally have an advantageous thermo-mechanical properties.
  • the tensile strength of the fully cured composition layer may be higher than 100 MPa and may be in the range of from about 120 MPa to 200 MPa or higher.
  • the ETB of the cured composition layers can be higher than 30 percent and may range from about 50 percent to 100 percent or higher.
  • the T g of the cured composition layer may be higher than 150 °C and can range from about 150 °C to 200 °C or higher. It should further be noted that the layers formed in this fashion from the composition of this invention also exhibit unusually high thermal decomposition temperature. Accordingly, the 5 percent weight loss temperature (T d5 ) of the cured polymeric layers is generally higher than 300 °C and can range from 300 °C to 420 °C or higher, thus offering hitherto unattainable properties.
  • exemplary applications for embodiments of the photosensitive compositions in accordance with the present invention include die attach adhesive, wafer bonding adhesive, insulation films (interlayer dielectric layers), protecting films (passivation layers), mechanical buffer films (stress buffer layers) or flattening films for a variety of semiconductor devices, and printed wiring boards.
  • Specific applications of such embodiments encompass a die-attach adhesive to form a single or multilayer semiconductor device, dielectric film which is formed on a semiconductor device; a buffer coat film which is formed on the passivation film; an interlayer insulation film which is formed over a circuit formed on a semiconductor device.
  • some embodiments in accordance with the present invention therefore provide a negative tone photosensitive polymer composition which exhibits enhanced characteristics with respect to one or more of mechanical properties (such as high tensile strength, elongation to break) and at least equivalent or better chemical resistance, as compared to alternate materials.
  • such embodiments provide generally excellent electrical insulation, adhesion to the substrate, and the like.
  • the photosensitive compositions of this invention can also be used to form adhesive layers for bonding the semiconductor chips to each other, such as in chip-stack applications.
  • a bonding layer used for such a purpose is composed of a cured product of the photosensitive adhesive composition of the present invention.
  • the adhesive layer is a single-layer structure, it can not only exhibit sufficient adhesiveness to the substrate but also it is expected to be free of significant stress resulting due to the curing step. Accordingly, it is now possible to avoid undesirably thick layer of film encompassing the chip as a laminate. Therefore, it should be noted that the laminates formed in accordance with the present invention are expected to be reliable in that the relaxation of stress concentration between layers caused by thermal expansion difference or the like can be obtained.
  • the semiconductor device having low height and high reliability can be obtained. That is, devices with low aspect ratio and low thickness can be obtained.
  • Such semiconductor device becomes particularly advantageous to electronic equipment, which has very small internal volume and is in use while carrying as a mobile device, for example. Even more advantageously, by practice of this invention it is now possible to form a variety of electronic devices featuring hitherto unachievable level of miniaturization, thinning and light-weight, and the function of the semiconductor device is not easily damaged even if such devices are subject to rugged operations such as swinging or dropping.
  • a cured product of the photosensitive adhesive composition of the present invention i.e., the adhesive layer or the film generally exhibits an indentation modulus of 2 to 4 GPa at 25°C.
  • the cured product of the photosensitive adhesive composition of the present invention exhibits an indentation modulus of 70 to 120% of the indentation modulus of the non-cured product at 25°C, i.e., before such curing step.
  • the photosensitive adhesive composition of the present invention exhibits an excellent adhesiveness to a suitable substrate, such as for example a semiconductor chip, and adhesiveness of 20 to 200 Newton (N) at 25°C can be achieved before curing and generally after etching and ashing process.
  • the photosensitive adhesive composition of the present invention may exhibit an indentation modulus at room temperature after curing which is relatively comparable to the indentation modulus of the uncured sample and not causing significant stress concentration between the semiconductor chips but contributing to forming of the adhesive layer with sufficient adhesiveness. Further, since the indentation modulus in a state before cured is within the predetermined range of indentation modulus after cured, and then, for example, it is not so possible that the photosensitive adhesive composition before cured is significantly deformed or flowed out, it is possible to increase the accuracy of alignment in laminating the semiconductor chips.
  • the electronic and/or the semiconductor device according to this invention encompass a laminated semiconductor element where said lamination consists of a photosensitive composition according to the present invention.
  • the semiconductor device encompassing a redistribution layer (RDL) structure further incorporates a photosensitive composition according to this invention.
  • the semiconductor device encompassing a chip stack structure further includes a photosensitive composition according to this invention.
  • the semiconductor device encompassing a complementary metal oxide semiconductor (CMOS) image sensor dam structure further incorporates a photosensitive composition according to this invention.
  • CMOS complementary metal oxide semiconductor
  • a film is formed by the photosensitive composition according to this invention.
  • such films generally exhibit excellent chemical, mechanical, elastic properties having a wide variety of utility in electronic, optoelectronic, microelectromechanical applications featuring excellent dielectric properties.
  • a microelectronic or optoelectronic device encompassing one or more of a redistribution layer (RDL) structure, a chip-stack structure, a CMOS image sensor dam structure, where said structures further incorporates a photosensitive composition according to this invention.
  • RDL redistribution layer
  • a method of forming a film for the fabrication of a microelectronic or optoelectronic device comprising:
  • the coating of the substrate with photosensitive composition of this invention can be performed by any of the coating procedures as described herein and/or known to one skilled in the art, such as by spin coating.
  • HFBAPP 4,4'-(((perfluoropropane-2,2-diyl)bis(4, 1-phenylene))bis(oxy))dianiline;
  • IRGACURE 369 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one;
  • BTMPTA (oxybis(methylene))bis(2-ethylpropane-2,l,3-triyl) tetraacrylate
  • TAEICY (2,4,6-trioxo-l,3,5-triazinane-l,3,5-triyl)tris(ethane-2,1-diyl) triacrylate;
  • FC-4432 - a non-ionic polymeric fluorochemical surfactant
  • the polyamic acid solution (127 g containing about 25 g polymer) thus obtained above was mixed with anhydrous pyridine (25 g), acetic anhydride (25 g) and cyclopentanone (100 g) and the solution heated to 90 °C for 4 hours under nitrogen atmosphere while stirring.
  • the reaction mixture was allowed to cool to ambient temperature and added to excess water/methanol (80/20) mixture (1.5 L) to isolate the polymer.
  • the gummy product was washed with excess (1 L) heptanes and dried in a vacuum oven at 80 °C for 24 hours to obtain a solid product (23 g, 92% isolated yield), which was characterized by GPC, 'H NMR and FT-IR.
  • a small sample of the polymer solution was also added to excess water/acetone (80/20) mixture to isolate the polymer for‘H NMR analysis.
  • the gummy product was washed with excess water/acetone (80/20) mixture and dried in a vacuum oven at 50 - 60 °C for 24 hours to obtain a solid product.
  • 'H-NMR (500 MHz) spectra measured in deuterated DMSO showed a broad peak centered at about 13.5 ppm for COOH and 10.99 ppm, 10.88 ppm, and 10.86 ppm for -NH- groups of the polyamic acid in approximately 1 : 1 ratio. Multiple peaks were observed at 6.7 - 8.7 ppm for the aromatic protons from 6FDA, PMDA PFMB and 6BF.
  • the polyamic acid solution (65 g containing about 11 g polymer) thus obtained was then mixed with anhydrous pyridine (11 g), acetic anhydride (11 g) and cyclopentanone (62 g) and the solution was heated to 90 °C for 6 hours under nitrogen atmosphere while stirring.
  • the reaction mixture was allowed to cool to ambient temperature and THF (25 g) was added.
  • This solution was added to excess water/methanol (80/20) mixture (1.7 L) to isolate the polymer.
  • the gummy product was washed with excess (1.2 L) water/methanol (80/20) mixture and dried in a vacuum oven at 70 °C for 24 hours to obtain a solid product (10.4 g, 95% isolated yield), which was characterized by GPC and 1 H NMR.
  • HFBAPP (7.78 g, 15 mmol) and PFMB (3.2 g, 10 mmol) were dissolved in NMP (76.2 g) and stirred at ambient temperature under a nitrogen atmosphere.
  • a mixture of 6FDA (5.41 g, 12.2 mmol), PMDA (2.66 g, 12.2 mmol) and IA (0.140 g, 1.25 mmol) was added in small batches to the above solution while stirring.
  • the reaction mixture was stirred at ambient temperature for 20 hours during which time the solution turned viscous.
  • An additional amount of NMP (21 g) was added to the viscous solution. A small portion of this solution was then diluted with DMAc for GPC analysis.
  • the polyamic acid solution (100 g containing about 16 g polymer) thus obtained above was mixed with anhydrous pyridine (16 g), acetic anhydride (16 g) and cyclopentanone (75 g) and the solution was heated to 90 °C for 6 hours under nitrogen atmosphere while stirring. The polymer became insoluble as the imidization progressed.
  • the polyamic acid solution (118 g containing about 20 g polymer) thus obtained above was mixed with anhydrous pyridine (20 g), acetic anhydride (20 g) and cyclopentanone (88 g) and the solution heated to 95 °C for 2 hours under nitrogen atmosphere while stirring. The polymer became insoluble as the imidization progressed.
  • Example 1 and Comparative Example 1 were dissolved in a solvent mixture of GBL and cyclopentanone solvent mixture (3: 1 weight ratio) to form respectively 20 weight percent solution for polymer of Example 1 and 15 weight percent solution for polymer of Comparative Example 1. Portions of these solutions were mixed with DCP (6 pphr) and filtered using 0.45 pm pore polytetrafluoroethylene (PTFE) disc filters. The polyimide polymer solutions from Example 1 and Comparative Example 1 containing no DCP were also filtered using 0.45 pm pore polytetrafluoroethylene (PTFE) disc filters.
  • PTFE 0.45 pm pore polytetrafluoroethylene
  • Photosensitive Compositions Thermo-mechanical Properties Isolated polyimide polymer from Example 1 was dissolved in a mixture of GBL/cyclopentanone (3: 1 weight ratio) to prepare 16 wt. % polymer solution. To this solution was added Irgacure-369 as a photo radical generator (10 pphr), CPTX as the photo-sensitizer (2 pphr), KBM-403E as the adhesion promoter (5 pphr) and FC-4432 as the surface leveling agent (0.3 pphr). This solution was then formulated into four different compositions by adding (DCP, 4 pphr) as a thermal radical initiator into two of these four compositions and also adding two different types of acrylate cross linkers as summarized in Table 2.
  • Irgacure-369 as a photo radical generator (10 pphr)
  • CPTX as the photo-sensitizer
  • KBM-403E the adhesion promoter
  • FC-4432 as the surface leveling agent
  • compositions thus formed in Examples 6A to 6D were filtered using 0.45 pm or 1 mm pore polytetrafluoroethylene (PTFE) disc filters. These compositions were spin coated on 4” bare Si wafers by spinning at 500 - 800 rpm for 30 seconds followed by post apply bake (PAB) at 1 10 °C for 3 minutes to generate films in 15 - 23 mm range. The films were then exposed using a broad band Hg-vapor light source (at 365 mn using a band pass filter) at an exposure dose of 1500 mJ/cm 2 . The exposed films were cured at 170 °C for 4 hours in an oven under nitrogen atmosphere.
  • PTFE polytetrafluoroethylene
  • the cured films were subsequently diced to 6 mm wide film strips and lifted out of the bare Si wafers by immersing in a dilute ( 1 wt. %) hydrogen fluoride (HF) solution in water.
  • HF hydrogen fluoride
  • Tensile and thermal properties were measured using Instron and TMA respectively. The results are summarized in Table 3. It is evident from the data presented in Table 3 that the use of DCP in the compositions of this invention as a thermal radical initiator increases both tensile strength and the glass transition temperature of the films so generated.
  • Isolated polyimide polymers from Comparative Example 1 and Example 2 were dissolved separately in a mixture of GBL and cyclopentanone (3: 1 weight ratio) to prepare 15 - 20 wt. % solutions.
  • Irgacure-369 as a photo radical generator (10 pphr)
  • CPTX as the photo-sensitizer (2 pphr)
  • BTMPTA as an acrylate cross linker (30 pphr)
  • KBM-403E as the adhesion promoter
  • FC-4432 as the surface leveling agent (0.3 pphr)
  • DCP dicumyl peroxide
  • Example 7A polymer of Comparative Example 1
  • Example 7B polymer of Example 1
  • Example 7C polymer of Example 2.
  • Each of the above three compositions were spin coated on 4” bare Si wafers by spinning at 300 - 800 rpm for 30 seconds followed by post apply bake (PAB) at 1 10 °C for 3 minutes to generate films having thickness in the range of 10 - 13 mm.
  • the films were then exposed using a broad band Hg-vapor light source (at 365 nm using a band pass filter) at an exposure doses of 3500 mJ/cm 2 (for Examples 7 A and 7B) or 1500 mJ/cm 2 (for Example 7C).
  • the exposed films were cured at 220 °C for 4 hours (for Examples 7 A and 7B) or 170 °C for 4 hours (for Example 7C) in an oven under nitrogen atmosphere.
  • compositions as formed above were spin coated on 4” SiO 2 wafers by spinning at 1300 - 1700 rpm for 30 seconds followed by post apply bake (PAB) at 110 °C for 3 minutes to generate films of thickness in 2 - 4 mm range.
  • the films were then exposed using a broad band Hg-vapor light source (at 365 mn using a band pass filter) at an exposure dose of 0 - 2500 mJ/cm 2 through a mask to generate negative tone images of lines, trenches, pillars and holes followed by a post exposure bake (PEB) at 110 °C for 2 minutes.
  • PEB post exposure bake
  • These films were immersed in cyclopentanone for 30 - 35 seconds to reveal the lines (L), pillars (P) and holes (H). Holes were not opened for the films from composition Examples 7A and 1C.
  • the photo imaging properties are summarized in Table 5.
  • FIG. 1 shows the top down view of the lines.
  • FIG. 2 shows the top down view of the pillars.
  • FIG. 3 shows the top down view of the holes.
  • composition 8A Polyamic acid polymer solution before isolation from Example 5 in NMP (15 wt. % solution) was used to prepare two photosensitive compositions, 9A and 9B.
  • Irgacure-369 as a photo radical generator (10 pphr)
  • CPTX as the photo-sensitizer (2 pphr)
  • BTMPTA as an acrylate cross linker
  • KBM-403E as the adhesion promoter
  • FC-4432 FC-4432 as the surface leveling agent
  • DPEH3MP (50 phr) was also added to composition Example 9B as a thiol cross linker.
  • Example 9A compositions were filtered using 0.45 mm pore polytetrafluoroethylene (PTFE) disc filters and kept refrigerated before use, and designated respectively as Example 9A (contained only BTMPTA as an acrylate cross linker) and Example 9B (contained BTMPTA as an acrylate cross linker and DPEH3MP as a thiol cross linker).
  • PTFE polytetrafluoroethylene
  • the polyamic acid solution (100 g containing 20 g polymer) thus obtained above was mixed with anhydrous pyridine (25 g) and acetic anhydride (25 g) and the solution heated to 90 °C for 4 hours under nitrogen atmosphere while stirring.
  • the reaction mixture was allowed to cool to ambient temperature and was added to excess water/acetone (80/20) mixture (1.5 L) to isolate the polymer.
  • the gummy product was washed with excess (1 L) heptanes and dried in a vacuum oven at 80 - 90 °C for 24 hours to obtain a solid product (18.2 g, 92% isolated yield), which was characterized by GPC, 'H NMR and FT-IR.

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Abstract

Des modes de réalisation de la présente invention concernent un acide polyamique ou des polymères de polyimide contenant un groupe terminal anhydride cyclique insaturé ainsi que des compositions photosensibles préparées à partir de ceux-ci qui sont utiles pour la formation de films à motifs pour créer des structures destinées à des dispositifs microélectroniques, des boîtiers microélectroniques, des systèmes microélectromécaniques, des dispositifs optoélectroniques et des afficheurs. Selon certains modes de réalisation, les compositions de la présente invention ont démontré présenter d'excellentes propriétés mécaniques non réalisables jusqu'à présent. Les images négatives formées à partir de celles-ci présentent des propriétés thermomécaniques améliorées, notamment des améliorations de propriétés.
PCT/US2020/021049 2019-03-05 2020-03-05 Acides polyamiques et polyimides coiffés par anhydride cyclique insaturé terminal et compositions photosensibles associées WO2020181022A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0540340A (ja) * 1991-08-07 1993-02-19 Asahi Chem Ind Co Ltd ポリイミドのパターン化方法
US20020093077A1 (en) * 2000-12-29 2002-07-18 Samsung Electronics Co. , Ltd Positive-type photosensitive polyimide precursor and composition comprising the same
US7485405B2 (en) 2004-10-07 2009-02-03 Shin-Etsu Chemical Co., Ltd. Photo-curable resin composition comprising a polyimide, a process for forming a pattern therewith, and a substrate protecting film
US8946852B2 (en) 2010-07-02 2015-02-03 Toray Industries, Inc. Photosensitive resin composition, photosensitive resin composition film, and semiconductor device using the photosensitive resin composition or photosensitive resin composition film
US20170298186A1 (en) * 2016-04-19 2017-10-19 Shin-Etsu Chemical Co., Ltd. Tetracarboxylic acid diester compound, polyimide precursor polymer and method for producing the same, negative photosensitive resin composition, positive photosensitive resin composition, patterning process, and method for forming cured film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0540340A (ja) * 1991-08-07 1993-02-19 Asahi Chem Ind Co Ltd ポリイミドのパターン化方法
US20020093077A1 (en) * 2000-12-29 2002-07-18 Samsung Electronics Co. , Ltd Positive-type photosensitive polyimide precursor and composition comprising the same
US7485405B2 (en) 2004-10-07 2009-02-03 Shin-Etsu Chemical Co., Ltd. Photo-curable resin composition comprising a polyimide, a process for forming a pattern therewith, and a substrate protecting film
US8946852B2 (en) 2010-07-02 2015-02-03 Toray Industries, Inc. Photosensitive resin composition, photosensitive resin composition film, and semiconductor device using the photosensitive resin composition or photosensitive resin composition film
US20170298186A1 (en) * 2016-04-19 2017-10-19 Shin-Etsu Chemical Co., Ltd. Tetracarboxylic acid diester compound, polyimide precursor polymer and method for producing the same, negative photosensitive resin composition, positive photosensitive resin composition, patterning process, and method for forming cured film

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